Phenoxyacetyl phosphonates



United States Patent 3,378,610 PHENOXYACETYL PHOSPHONATES Delta W. Gier, Parkville, Mo., assignor to Chemagro Corporation, New York, N.Y., a corporation of New York No Drawing. Continuation-impart of application Ser. No. 412,263, Nov. 18, 1964. This application Apr. 20, 1965, Ser. No. 449,640

12 Claims. (Cl. 260--940) AESTRACT OF THE DISCLOSURE Compounds are provided, which are useful as herbicides, defoliants and desiccants, having the formula (ROMP CH2O R where R is alkyl of up to 18 carbon atoms, phenyl, alkyl phenyl, chloroalkyl and cyanoalkyl and R is rnono, di and trihalophenyl and monohalo monomethyl phenyl.

The present application is a continuation-in-part of application Ser. No. 412,263 filed Nov. 18, 1964.

This invention relates to novel phosphonates and their use as herbicides, de-foliants and desiccants.

It is an object of the present invention to prepare new phosphonates.

Another object is to prepare improved compositions and processes for killing undesired plants.

An additional object is to prepare post-emergent herbicides.

A further object is to prepare pre-emergent herbicides.

Yet another object is to prepare formulations showing selective activity as pro-emergent and post-emergent herbicides.

A still further objective is to desiccate plants, particularly cotton.

Another object is to defoliate plants, particularly cotton.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that these objects can be attained by preparing phosphonates of the formula where R is alkyl, preferably lower alkyl, or phenyl, or alkyl phenyl, or haloalkyl or cyanoalkyl or phenyl, or alkyl phenyl and R is mono, di or trihalophenyl or halo methyl phenyl. The preferred halogen is chlorine. Compounds having the above formula exhibit herbicidal properties. Examples of compounds Within the present invention include 0,0-dimethyl-4-chlorophenoxyacetyl phosphonate, 0,0-dimethyl-Z-chlorophenoxyacetyl phosphonate,

0,0-dimethyl-2-methyl-4-chlorophenoxyacetyl phospho nate, 0,0-dimethyl-2,4-dichlorophenoxyacetyl phosphonate, 0,0-dimethyl-2,4,S-trichlorophenoxyacetyl phosphonate, 0,0-dimethyl-2,4,S-tribromophenoxyacetyl phosphonate, 0,0-dimethyl-2,4-dichloro-5-bromophenoxyacetyl phosphonate, 0,0-dimethyl-Z,4,5-trifiuorophenoxyacetyl phosphonate, 0,0-diethyl-2-chlorophenoxyacetyl phosphonate, 0,0-diethyl-4-chlorophenoxyacetyl phosphonate, 0,0-diethyl-3-chlorophenoxyaoetyl phosphonate, 0,0-diethyl-2,4-dichlorophenoxyacetyl phosphonate, 0,0-diethyl-2,6-dicl1lorophenoxyacetyl phosphonate, 0,0-diethyl-3,4-dichlo-rophenoxyacetyl phosphonate, 0,0-diethyl-2,4,S-trichlorophenoxyacetyl phosphonate, 0,0-diethyl-2,4,5-triiodophenoxyacetyl phosphonate, 0,0-diethyl-2-methyl-4-bromophenoxyacetyl phosphonate, 0,0-diethyl-2-methyl-4-chlorophenoxyacetyl phosphonate, 0,0-diethyl-2,3,4-trichlorophenoxyacety1 phosphonate, 0,0-diethyl-2,4,fi-trichlorophenoxyacetyl phosphonate, O-methyl-O-ethyl-2,4,S-trichlorophenoxyacetyl phosphonate, 0,0-dipropy1-4-chlorophenoxyacetyl phosphonate, 0,0-dipropyl-Z-chlorophenoxyacetyl phosphonate, 0,0-dipropyl-2,4,5-tri-chlorophenoxyacetyl phosphonate, 0,0-diisopropyl-Z-chlorophenoxyacetyl phosphonate, 0,0-di-n-butyl-Z-methyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-n-butyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-n-butyl-Z-chlorophenoxyacetyl phosphonate, 0,0-di-n-butyl-2,4,S-trichlorophenoxyacetyl phosphonate, 0,0-dia myl-Z-rnethyl-4-chlorophenoxyacetyl phosphonate, 0,0-di(2-ethy1hexyl)-(Z-chlorophenoxyacetyl) phosphonate, 0,0-di-(2-ethylhexyl)-(4-chlorophenoxyacetyl) phosphonate, 0,0-di- (Z-ethylhexyl) (Z-methyl-4-ch1lorophenoxyac etyl) phosphonate, 0,0-di- (Z-ethylhexyl)-(2,4,S-trichlorophenoxyacetyl) phosphonate, 0,0-diisooctyl-Z,4,S-trichlorophenoxyacetyl phosphonate, 0,0-di-n-octy1-4-chlorophenoxyacetyl phosphonate, 0,0-dilauryl-Z-chlorophenoxyacetyl phosphonate, 0,0-dipheny1-4-chlorophenoxyacetyl phosphonate, 0,0-diphenyl-2-chlorophenoxyacetyl phosphonate, 0,0-diphenyl-2,4,S-trichlorophenoxyacetyl phosphonate, 0,0-diphenyl-Z-methyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-p-tolyl-2-chlorophenoxyacetyl phosphonate, 0,0-di-o-tolyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-m-tolyl-2,4,S-trichlorophenoxyacetyl phosphonate, 0,0-di-o-butylphenyl-2-methyl-4-chlorophenoxyacetyl phosphonate, O,O-di-2,-cl1loroethyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-3-chloropropyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-5'-chloroamyl-4-chlorophenoxyacetyl phosphonate, 0,0-diisopropyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-2-chloroethyl-Z-chlorophenoxyacetyl phosphonate,

3 0,0-di-2-cyanisopropyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-3-cyanopropyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-6-cyanohexyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-octadecyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-p-octylphenyl-4-chlorophenoxyacetyl phosphonate, 0,0-di-2'-chloroethy1-2-methyl-4-chlorophenoxyacetyl phosphonate, 0,0-diisopropyl-2-methyl-4-chlorophenoxyacetyl phosphonate, 0,0-2'-cyanisopropyl-Z-methyl-4-chloro-phenoxyacetyl phosphonate, 0,0-dihexyl-2-methyl-4-chlorophenoxyacetyl phosphonate, 0,0-diisoocty-l-2-methyl-4-chlorophenoxyacetyl phosphonate, 0,0-dioctadecyl-2-methyl-4-chiorophenoxyacetyl phosphonate, 0,0-di-p-octylphenyl-2-methyl-4-chlorophenoxyacetyl phosphonate, 0,0-dimethyl-2,4-dichlorophenoxyacetyl phosphonate, 0,0-di-2-chloroethyl-2,4-dichlorophenoxyacetyl phosphonate, 0,0-diisopropy1-2,4-dichlorophenoxyacetyl phosphonate, 0,0-di-2-cyanoisopropyl-2,4-dichlorophenoxyacetyl phosphonate, 0,0-din-butyl-2,4-dichlorophenoxyacetyl phosphonate, 0,0-dihexyl-2,4-dichlorophenoxyacetyl phosphonate, 0,0-diisooctyl-2,4-dichlorophenoxyacetyl phosphonate, 0,0-di-2'-ethylhexyl-2,4-dichlorophenoxyacetyl phosphonate, 0,0-dioctadecyl-2,4dichlorophenoxyacetyl phosphonate, 0,0diphenyl-2,4-dichlorophenoxyacetyl phosphonate, 0,0-di-2-chloroethyl-2,4,S-trichlorophenoxyacetyl phosphonate, 0,0-diisopropyl-2,4,S-trichlorophenoxyacetyl phosphonate, 0,0-di-2'-cyanoisopropyl2,4,5-trichlorophenoxyacetyl phosphonate, 0,0-dihexyl-2,4,S-trichlorophenoxyacetyl phosphonate, 0,0-dioctadecyl-2,4,5-trich1orophenoxyacetyl phosphonate, 0,0-di-p-octylphenyl-2,4,S-trichlorophenoxyacetyl phosphonate.

The new compounds of the present invention are prepared by the following procedures.

Procedure A A known quantity of the phenoxyacctyl chloride is placed in a reaction flask equipped with a mechanical stirrer, condenser and dropping funnel. (Solid acid chlorides were dissolved in a minimum of dry benzene while liquid acid chlorides were reacted Without solvent.) Slightly more than an equimolar quantity of the desired trialkyl phosphite was added dropwise to the phenoxy acetyl chloride with vigorous stirring. for 0.1 molar quantities, 20 to 30 minute periods were necessary for addition of the phosphite. In all cases, the reaction rates were relatively high and easily observable by liberation of heat. Following the addition of the phosphite, the reaction mixture was heated to 80100 C. for 23 hours.

A vacuum was then applied to the reaction flask (0.5 1.0 mm. pressure) and the product was stripped at a pot temperature of 110150 C. All of the products obtained were clear to pale red oils, or semi-solids of high solubility in most organic solvents.

The essence of the above procedure is reacting the phenoxyacetyl chloride with a trialkyl phosphite and removing the organic chloride formed, preferably under reduced pressure.

Procedure B A known quantity of the phenoxyacetyl chloride was placed in the reaction flask. (Solid acid chlorides were dissolved in a minimum of dry benzene while no solvent was used with liquid acid chlorides.) Slightly more than an equimolar quantity of the desired dialkyl hydrogen phosphite or diaryl hydrogen phosphite was added dropwise to the phenoxy acetyl chloride with vigorous stirring. For 0.1 molar quantities, 20 to 30 minute periods were necessary for addition of the phosphite. In all cases, the reaction rates were relatively high and easily observable by liberation of heat. Following addition of the phosphite, aspirator vacuum (5075 mm. pressure) was applied to the reaction flask through the condenser and the reaction mixture was heated to -1 10 C. for 2-3 hours.

A vacuum (0.51 mm. pressure) was then applied to the reaction flask and the product was stripped at a pot temperature of 1l0l50 C. All of the products obtained were clear to pale red oils, or semi-solids having a high solubility in most organic solvents.

The essence of Procedure B is reacting the phenoxy acetyl chloride with a dialkyl or diaryl hydrogen phosphite and removing the hydrogen chloride formed, preferably under reduced pressure.

The 0,0-dialkyl phosphonates can be prepared by either Procedure A or Procedure B. The 0,0-diaryl phosphonates can be prepared only by Procedure B.

Illustrative of starting phenoxy acetyl chlorides are 2- chlorophenoxy acetyl chloride, 4-chlorophenoxy acetyl chloride, 2,4-dichlorophenoxy acetyl chloride, 2,4,5-trichlorophenoxy acetyl chloride, 2,4,5 tribromophenoxy acetyl chloride, 2,4,5-tribromophenoxy acetyl bromide, 2- methyl-4-chlorophenoxy acetyl chloride.

Illustrative of starting phosphites for Procedure A are trimethyl phosphite, triethy-l phosphite, dimethyl ethyl phosphite, tripropyl phosphite, triisopropyl phosphite, trin-butyl phosphite, trihexyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, tri (Z-ethyl hexyl) phosphite, and trilauryl phosphite.

Illustrative starting phosphites for Procedure B are dimethyl hydrogen phosphite, diethyl hydrogen phosphite, dipropyl hydrogen phosphite, diisopropyl hydrogen phosphite, di-n-butyl hydrogen phosphite, di-Z-ethyl hexyl hydrogen phosphite, dipheny-l hydrogen phosphite, di-p-tolyl hydrogen phosphite.

Unless otherwise indicated all parts and percentages are by weight.

Example 1 10.25 grams (0.05 mole) of p chlorophenoxy acetyl chloride was treated according to Procedure A with 6.2 grams (0.05 mole) of trimethyl phosphite to give 6.7 grams (48% yield) of 0,0-dimethyl-4-chlorophenoxy acetyl phosphonate as a clear oil; 11 1.4965; percent Cl 11.3 (12.7 theory); percent P 11.8 (11.1 theory).

Example 2 10.25 grams (0.05 mole) of p-chlorophenoxy acetyl chloride was treated according to Procedure A with 8.3 grams (0.05 mole) of triethyl phosphite to give 11.0 grams (72% yield) of 0,0-diethyl-4-chlorophenoxy acetyl phosphonate as a clear oil; u 1.4955; percent Cl 10.6 (theory 11.2); percent P 10.4 (theory 10.0).

I Example 3 10.25 grams (0.05 mole) of p-chlorophenoxy acetyl chloride was treated according to Procedure A with 12.5 grams (0.05 mole) of tri-n-outyl phosphite to give 14.3 grams (78% yield) of 0,0-di-n-butyl-4-chlorophenoxy acetyl phosphonate as a clear oil; 11 1.4904; percent CI 9.4 (theory 9.7); percent P 8.4 (theory 8.5).

Example 4 10.25 grams (0.05 mole) of p-chlo-rophenoxy acetyl chloride was treated according to Procedure B with 11.7 grams (0.05 mole) of diphenyl hydrogen phosphite to give 15.3 grams (75% yield) of 0,0-diphenyl-4-chlorophenoxy acetyl phosphonate as a clear oil; 11 1.5740; percent CI 9.1 (theory 8.8); percent P 8.1 (theory 7.7).

Example 5 10.25 grams (0.05 mole) of O-chlorophenoxy acetyl chloride was treated according to Procedure A with 6.2

grams (0.05 mole) of trimethyl phosphite to give 11.0

grams (78.6% yield) of 0,0-din1ethyl-2-chlorophenoxy acetyl phosphonate as a clear oil; n 1.5185; percent CI 13.6 (theory 12.7); percent P 10.4 (theory 11.1).

Example 6 10.25 grams (0.05 mole) of O-chlorophenoxy acetyl chloride was treated according to Procedure A with 12.5 grams (0.05 mole) of tri-n-butyl phosphite to give 15.9 grams (78.3% yield) of 0,0-di-n-butyl-2'chlorophenoxy acetyl phosphonate as a clear oil; 11 1.4895; percent Cl 9.2 (theory 9.7); percent P 8.8 (theory 8.5).

Example 8 10.25 grams (0.05 mole) of O-chlorophenoxy acetyl chloride was treated according to Procedure B with 11.7 grams (0.05 mole) of diphenyl hydrogen phosphite to give 15 grams (74% yield) of 0,0-diphenyl-2-chlorophenoxy acetyl phosphonate as a light yellow oil; n 1.5703; percent C1 8.4 (theory 8.8); percent P 7.5 (theory 7.6).

Example 9 13.8 grams (0.05 mole of 2,4,5-trichlorophenoxy acetyl chloride was treated according to Procedure A with 6.2 grams (0.05 mole) of trimethyl phosphite to give 13.0 grams (74.9% yield) of 0,0-dimethyl-2,4,S-trichlorophenoxy acetyl phosphonate as a White semi-solid; 21 1.5012; percent Cl 33 (theory 31); percent P 8.3 (theory 8.8).

Example 10 53.6 grams (0.2 mole of 2,4,5-trichlorophenoxy acetyl chloride was treated according to Procedure A with 33.2 grams (0.2 mole) of triethyl phosphite to give 65 grams (95.6% yield) of 0,0-diethyl2,4,5-trichlorophenoxy acetyl phosphonate as a pale yellow semi-solid; n 1.5015; percent CI 28.5 (theory 28.2); percent P 8.2 (theory 8.3).

Example 11 13.8 grams (0.05 mole) of 2,4,5-trichlorophenoxy acetyl chloride was treated according to Procedure A with 15.0 grams (0.06 mole) of tri-n-butyl-phosphite to give 20.6 grams (80% yield) of 0,0-di-n-butyl-2,4,5-trichlorophenoxy acetyl phosphonate as a clear oil; 11 1.4950; percent Cl 23.8 (theory 24.5); percent P 7.8 (theory 7.2).

Example 12 13.8 grams (0.05 mole) of 2,4,5-trichlorophenoxy acetyl chloride was treated according to Procedure B with 11.7 grams (0.05 mole) of diphenyl hydrogen phosphite to give 16.6 grams (70% yield) of 0,0-diphenyl-2,4,5- trichlorophenoxy acetyl phosphonate as a pale yellow semi-solid; n 1.5715; percent Cl 19.5 (theory 22.5); percent P 7.2 (theory 6.6).

Example 13 11.55 grams (0.05 mole) of 2-methyl-4-chlorophenoxy acetyl chloride was treated according to Procedure A with 6.2 grams (0.05 mole) of trimethyl phosphite to give 14.3 grams (98% yield) of 0,0-dimethy1-2-methyl- 4-chlorophenoxy acetyl phosphonate as a pale yellow oil,

6 n 1.5106; percent Cl 12.8 (theory 12.1); percent P 10.3 (theory 10.6).

Example 14 20.1 grams (0.1 mole) of 2-methyl-4-chlorophenoxy acetyl chloride was treated according to Procedure A with 20 grams (0.12 mole) of triethyl phosphite to give 29.4 grams (99% yield) of 0,0-diethyl-2-methyl-4-chlorophenoxy acetyl phosphonate as a pale pink oil; 11 1.5015; percent CI 10.6 (theory 1.1.6); percent P 10.0 (theory 10.1).

Example 15 11.55 grams (0.05 mole) of 2-methyl-4-chlorophenoxy acetyl chloride was treated according to Procedure A with 12.5 grams (0.05 mole) of tri-n-butyl phosphite to give 18.6 grams (99% yield) of 0,0-di-n-butyl-2-methyl- 4-chlorophenoxy acetyl phosphonate as a clear oil; n 1.4974; percent Cl 9.7 (theory 9.4); percent P 7.9 (theory 8.3).

Example 16 11.55 grams (0.05 mole) of 2-methyl-4-chlorophenoxy acetyl chloride was treated according to Procedure B with 11.7 grams (0.05 mole) of diphenyl hydrogen phosphite to give 19.3 grams (93% yield) of 0,0-diphenyl-2-methy1-4-chlorophenoxy acetyl phosphonate as a clear oil; n 1.5680; percent Cl 8.5 (theory 8.5); percent P 8.2 (theory 7.4).

Example 17 10.25 grams (0.05 mole) of o-chlorophenoxy acetyl chloride was treated according to Procedure B with 15.3 grams (0.05 mole) of di-Z-ethyl hexyl hydrogen phosphite to give 17.8 grams (75% yield) of 0,0-di-2-ethyl hexyl-2-chlorophenoxy acetyl phosphonate as a clear oil; 11 1.4860; percent Cl 7.2 (theory 7.5); percent P 6.2 (theory 6.5).

Example 18 10.25 grams (0.05 mole) of p-chlorophenoxy acetyl chloride was treated according to Procedure B with 15.3 grams (0.05 mole) of di-Z-ethyl hexyl hydrogen phosphite to give 17.8 grams (75% yield) of 0,0-di-2-ethyl hexyl-4-ch1orophenoxy acetyl phosphonate as a clear oil; n 1.4839; percent CI 6.7 (theory 7.5); percent P 6.6 (theory 6.5).

Example 19 11.55 grams (0.05 mole) of 2-methyl-4-chlorophenoxy acetyl chloride was treated according to Procedure B with 15.3 grams (0.05 mole) of di-2-ethyl hexyl hydrogen phosphite to give 21 grams yield) of 0,0-di-(2- ethyl hexyl)-(2-methyl-4-chlorophenoxy acetyl) phosphonate as a clear oil; 11 1.4858; percent Cl 7.0 (theory 7.2); percent P 5.5 (theory 6.3).

Example 20 13.8 grams (0.05 mole) of 2,4,5-trichlorophenoxy acetyl chloride was treated according to Procedure B with 15.3 grams (0.05 mole) of di-Z-ethyl hexyl hydrogen phosphite to give 15.8 grams (58% yield) of 0,0-di-(2-ethyl hexyl)-(2,4,5-trichlorophenoxy acetyl) phosphonate as a clear oil; 22 1.4875; percent Cl 18.8 (theory 19.6); percent P 6.7 (theory 5.7).

Using Procedure A with the appropriate substituted phenoxyacetyl phosphite and the appropriate trialkyl or tri substituted alkyl phosphite, e.g. tris (Z-chloroethyl) phosphite, tris (Z-cyanoisopropyl) phosphite, tris octadecyl phosphite there were obtained as shown in Table A the indicated chlorophenoxy acetyl phosphonates where X and Y indicated the substituents on the phenoxy group and R and R indicate the groups attached to the two available oxygens of the phosphonate. As indicated in the table, R and R were the same.

Using Procedure B in similar fashion there were obtained the indicated phosphonates wherein R and R were aryl.

TABLE A Percent Percent 01 Percent P X Y R and R Yield Found Theory Found Theory 4-chloro 2-chloroethyl 98 27. 9 28. 3 7. 9 8. 2 Do. Isopropyl 92 10. 6 10. 6 9. 3 9. 3 Do. 2-cyanoisopropyl 91 9. 9 9. 5 7. 1 8. 3 D0. 93 8. 6 S. 5 7. 1 7. 4 Do... 92 7. 8 7. 5 6. 6. Do... 99 7. 5 7. 5 6. 6 6. 5 Do.-. p-Octylphenyl. 99 9. 5 8. 7 6. 7 7. 6 2'chloroethyll 99 28. 6 27. 4 7. 5 7. 9 88 11. 0 10. 2 8. 7 8. 9 67 11. 4 9. 1 7. 0 7. 9 99 9. 0 8. 2 6. 5 7. 1 72 8. 0 7. 3 7. 3 6. 3 99 4. 1 4. 6 3. 7 4. 0 99 10. 1 7. 9 6. 3 6. 9 89 22. 3 22. 7 9. 7 9. 9 93 19. 8 21. 0 9. 2 9. 2 98 34. 6 34. 8 7. 4 7. 6 84 18. 4 l9. 2 9. 0 8. 4 94 16. 6 17. 4 7. 3 7. 6 98 18. 1 17. 9 7. 8 7. 8 97 16. 8 15. 7 6. 6 6. 8 97 14. 6 14. 0 5. 6 6. 1 78 13. 0 14. 0 6. 8 6. 1 99 8. 3 9. 0 3. 7 3. 9 92 12. 4 14. 9 6. 6 6. 5 84 17. 0 16. 2 7. 8 7. 1 85. 3 38. 6 39. 9 7. O 7. 0 69 29. 7 26. 5 6. 7 7. 7 52 21. O 25. 1 5. 1 7. 3 69 19. 6 21. 8 6. 5 6. 4 S1 17. 5 19. 6 G. 0 5. 7 99 14. 2 13. 0 3. 7 3. 8 73 21.1 20. 9 6. 3 6. 1

The compounds of the present invention can be used alone as herbicides, defoliants or desiccants but it has been found desirable to apply them together with inert solids to form dusts, or more preferably suspended in a suitable liquid diluent, preferably water. There can also be added surface active agents and inert solids in such liquid formulations. Desirably, 0.051% by weight of surface active agent is employed. The active ingredient can be from 0.01 to 95% by weight of the entire composition in such cases.

In place of water there can be employed organic solvents as carriers, e.g. hydrocarbons such as benzene, toluene, xylene, kerosene, diesel oil, fuel oil, and petroleum naphtha, ketones such as acetone, methyl ethyl ketone and cyclohexanone, chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene and perchloroethylene, esters such as ethyl acetate, amyl acetate and butyl acetate, others, e.g. ethylene glycol monomethyl ether and diethylene glycol monomethyl ether, alcohols, e.g. ethanol, isopropanol and amyl alcohol, etc.

The herbicides, defoliants and desiccants of the present invention can also be applied with inert herbicidal adjuvants or carriers such as talc, pyrophyllite, synthetic fine silica, attaclay, kieselguhr, chalk, diatornaceous earth, lime, calcium carbonate, bentonite, fullers earth, cottonseed hulls, wheat flour, soyabean flour, pumice, tripoli, wood flour, walnut shell flour, redwood flour and lignin.

It is frequently desirable to incorporate a surface active agent in the herbicidal, defoliant or desiccant compositions of this invention. Such surface active agents, i.e., wetting agents, are advantageously employed in both the solid and liquid compositions. Th surface active agent can be anionic, cationic or nonionic in character.

Typical classes of surface active agents include alkyl sulfonate salts, alkylaryl sulfonate salts, alkyl sulfate salts, alkylamide sulfonate salts, alkylaryl polyether alcohols, fatty acid esters of polyhydric alcohols and the alkylene oxide addition products of such esters, and addition products of long chain mercaptans and alkylenc oxides. Typical examples of such surface active agents include the sodium alkyl benzene sulfonates having 14 to 18 carbon atoms in the alkyl group, alkylphenolethylene oxide condensation products, e.g. p-isooctylphenol condensed with ethylene oxide units, soaps, e.g. sodium stearate and potassium oleate, sodium salt of propylnaphthalene sulfonic acid, (di-Z-ethyl hexyl) ester of sodium sulfosuccinic acid, sodium lauryl sulfate, sodium salt of the sulfonated monoglyceride of cocoanut fatty acids, sorbitan sesquioleate, lauryl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, polyethylene glycol lauryl ether, polyethylene esters of fatty acids and rosin acids, e.g. Ethofat 7 and 13, sodium N-methyl- N-oleyltaurate, Turkey red oil, sodium dibutylnaphthalene sulfonate, sodium lignin sulfonate (Marasperse N), polyethylene glycol stearate, sodium dodecylbenzene sulfonate, tertiary dodecyl polyethylene glycol thioether (Nonionic 218), long chain ethylene oxide propylene oxide condensation product, e.g. Pluronic 61, sorbitan monolaurate, polyethylene glycol ester of tall oil acids, sodium octylphenoxyethoxyethyl sulfate, tris (polyoxyethylene) sorbitan monostearate (Tween 60), sodium dihexyl sulfosuccinate.

The solid and liquid formulations can be prepared by any of the conventional methods. Thus the active ingredient can be mixed with the solid carrier in finely divided form in amounts small enough to preserve the free-flowing property of the final dust composition.

When using the compounds as defoliants or desiccants, they of course should be used in an amount less than that which will have a herbicidal effect on the plants to be defoliated or desiccated. While the compounds are primarily useful in the defoliant and desiccant field with cotton, they can also be employed to defoliate or desiccate other crops such as beans for example.

In the following examples or tables illustrating herbicidal activity the phosphonates were formulated into the following pre-mix, the parts being expressed by volume.

8 parts of a mixture of mono-, diand tri-methyl naphthalenes (Velsicol AR 50 G).

1 part butyl carbitol acetate.

1 part Triton X 161 (a mixture of p-octylphenolethylene oxide adduct containing about 16 ethylene oxide units together with a sodium alkylphenol sulfonate).

Two pounds per gallon of the test chemical were added to this pre-rnix.

In the pro-emergent herbicide tests the efiiciency of the candidate was measured by planting the indicated plants in soil and spraying the surface of the soil with the chemical the same day the plants are planted.

In the post-emergent herbicide test, the plants were allowed to grow for 10-14 days prior to application of the herbicides.

In the following tables the effect of the herbicide is mentioned on the scale from 0-10 where 0 is no effect and 10 emergent herbicides. pounds including 0,0-

Oats

Beau Wheat complete herbicide effect, namely 100% dead plants. ing Tables 3, 4, 5, and 6. As can be seen from the Tables In the tables the rates are expressed in pounds of active 3-6, the compounds of the present invention show selecingredient per acre. tive activity as pre-emergent and post- Table 1 is a preliminary post-emergent herbicide test Furthermore, several of the com and Table 2 is a preliminary pro-emergent herbicide test. 5 dimethyl (2,4,5 trichlorophenoxy acetyl) phosphonate,

TABLE 1 R Rate Flax Sugar Rad.

Beets Oats Bean Wheat Rad.

Sugar Beets TABLE 2 Rate Flax phenoxy acetyl) phospho- S-trichlorophenoxy acetyl) phos- (4-ch1orophenoxy acetyl) phosphoy acetyl) phosphoy acetyl) phospho- 4-chlorophenoxy acetyl) idal activity on broad leaf y a marked retardation of growth Wheat Flax compounds within the formula, as set forth in the followm m m m m m m m m m m u m m "nun" "Dunn" n ""mn nnnnnu "w. -x e n "Lu unuuun 1.v.l1 l1. yv. YIOOO m n m w. w m m 1y m n h m n m a a a me n mmmemm nm nun MEwmM PMEmPM nrammm m m m m m m m n m n 0 N n n n u n -v- -o-- "....1. unuan .....v.. .n..... .....8..... .1... 1 .y... V. ...n. D nun w...... w. n hnunLl h m wtnnu nw .u m v.v. m m u n u n w n u m m w m a un" numhun rnumw m m D... mama anamamamammm mono nmonnmonommm h I h hhh; c e wee 4r 2 4. 2442 TABLE 6.-SECONDARY SCREENING-PRE-EMERGENCE ACTIVITY Snap Sugar R R Rate Oats Cuc. Beans Corn Wheat Flax Cotton Bad. Beets Alfalfa 4-eh1orophenyl Methyl 4 3 8 9 2 9 8 9 8 8 2 6 6 7 0 0 7 3 8 9 6 1 2 8 0 0 7 5 0 6 6 Do. Ethyl 4 4 8 7 0 4 8 8 s 5 5 2 0 7 7 0 2 8 5 8 7 4 6 4 7 6 2 7 3 7 6 6 D0 n-Butyl 4 0 7 8 0 3 8 5 S 6 7 0 6 7 6 2 7 3 7 7 4 0 5 6 0 6 6 1 6 6 4 Do- Phenyl 4 6 6 8 6 6 7 4 s 7 6 2 6 4 7 6 0 6 0 6 4 6 1 0 3 6 0 0 6 1 7 5 2 2,4,5-trl6hlorophenyl Methyl 4 5 7 9 2 4 8 0 8 7 8 2 0 6 6 1 6 7 6 7 8 9 V 1 6 6 7 6 6 6 6 1 6 7 Do Ethyl 4 0 3 0 0 0 4 1 0 6 7 7 2 6 2 6 6 6 2 6 5 6 4 1 6 6 6 0 6 6 0 6 6 6 Don-Butyl 4 6 4 8 6 6 6 6 7 6 6 2 6 2 5 0 6 5 6 5 6 7 1 6 2 6 6 6 4 6 2 6 0 Do Phenyl 4 3 7 6 6 6 7 6 7 6 16 2 6 1 4 0 6 7 6 5 6 6 1 6 6 0 0 6 6 0 5 4 7 4-ehloro-2-methylphenyl Methyl 4 6 8 7 4 7 8 9 10 10 10 2 5 8 5 2 6 6 6 16 16 16 1 3 7 3 6 6 6 6 16 6 16 Do Ethyl 4 2 6 6 4 7 7 6 6 6 1o 2 1 7 7 2 6 7 6 10 6 6 1 6 7 7 1 5 5 8 9 8 6 Do n-Butyl 4 5 7 3 2 4 8 6 16 16 16 2 6 6 4 6 6 7 6 6 6 6 1 6 7 5 1 4 6 6 6 7 6 D0 Phenyl 4 6 8 4 2 4 8 6 16 16 10 2 6 8 6 6 4 5 7 6 6 6 1 6 6 1 6 6 4 6 6 6 6 4-ch1orophenyl 2-ethyl hexyl 4 1 3 7 0 4 7 4 7 6 5 2 1 4 6 6 1 6 3 6 4 6 1 0 6 6 6 1 5 2 6 6 6 4-ehloro-2-methylphenyl d0 4 3 7 6 2 5 8 9 9 9 16 2 2 6 6 6 5 6 7 6 6 6 1 1 6 2 1 4 7 6 9 6 6 2,4,5trlehlorophenyl .do 4 6 6 3 0 0 8 3 6 9 10 2 6 6 5 6 6 9 6 5 3 8 1 6 2 6 0 0 5 1 2 2 5 In the followmg table lllus tratmg defohant and deslcare set forth m Table 7. The compounds employed 1n cant activity, the phosphonates were formulated mto a Table 7 had the formula mixture oontammg 0.5 gram of the test chennoal 1n ml. of acetone eon-talmng /2% of Tween 20 [tns (poly- C") fi/OR oxyethylene) sorbltan mono laur-a'te]. Th1s m1xture was 40 OCHQC P sprayed on cotton plan-ts 1n the fiowenng stage of development uslng the 1nd1ca'ted dosages 1n pounds of actlve XX n o D m-gred1ent per acre. Observe-110116 were made 7 days after spraying the plants. In some mstances only the deslccahon where n 16 an mteger from 1 to 3, X 1'6 chlorme, Y 16 effect was reeorded and in other cases the results of hydrogen or methyl and the unspecrtied carbon atoms of both defoliation and des1cca1t1on were noted. The results the benzene rmg are attached to hydrogen.

TABLE 7 X Y R and R Rate Percent Percent (lbsJaere) Defollatlon Desiecetion 4-chloro Hydrogen Methyl g 2%.; 22 D0 .do Ethyl 8 10.5 65 2 6.6 56 Do do.. n-Butyl. 8 U 2 6 66 Do ..do 2-ethylhexyl 8 0 45 Do dn Phenol 8 67 2 6 46 2-ehlor0 do Ethyl 8 0 35 2 6 25 Do n-Butyl g 50 Do d 2'-ethy1hexyl 8 28.6 50 Do do Phenyl g 69 20 4-eh1oro 2-methyl Methyl 3 8 8 Do dn Ethyl 8 11.8 76 2 6.3 76 Do do n-Butyl 8 0 5 2 6 Do do 2'-ethylhexyl 8 0 56 Do do Phenyl 8 6 76 2 6 55 2,4,5-trichloro Hydrogen Methyl g 3 3 8 6 80 2 6 55 8 6 7O 2 6 6 6 76 2 12.5 8 6 75 2 6 75 TABLE 7.Continued X Y R and R Rate Percent Percent (lbs/acre) Defoliatlon Desiceation do 2-chloroethyl 8 45 2 Do do Isopropyl 8 2 Do Z-methyl 2'-chl0roethy1 8 2 50 Do .do Isopropyl 8 65 2 35 D0 .do Octadecyl 8 10 2,4-dichloro l Hydrogen Methyl.-." e, 8 95 2 Do .do Ethyl 8 2 60 Do .do Isopropyl 8 95 2 95 Do .do 2-chloroethyl 8 50 2 50 Do .do n-Butyl 8 2 65 Do do 2-ethy1hexyl 8 80 2 65 Do .-do Octadecyl 8 30 Do d0 Phenyl 8 80 2 60 2,4,5-trichloro .-do 2 -chloroethyl 8 45 2 35 Do Hydrogen Isopropyl 8 80 2 60 Do Hydrogen Octadecyl 8 30 I claim: 7. 0,0-di lower alkyl mono methyl mono chloro- 1. A compound having the formulal ll (ROMPCCHzOR acetyl phosphona'te having up to 18 carbon atoms in the 45 :alkyl group.

phenoxya cetyl phosphonate.

8. 0,0-diphenyl mono methyl mono chl-orophenoxy aoetyl phosphon'ate.v

9. 0,0-di (chloro lower alkyl) mono to tri chlorophenoxy acetyl phosphonate.

10. 0,0-di (chloro lower alkyl) mono methyl mono chlorophenoxy acetyl ph-os-phonate.

11. 0,0-di (cyano lower alkyl) mono to tri chlorophenoxy acetyl phosphonate.

12. 0,0-di (cyano lower alkyl) mono methyl mono chlorophenoxy acetyl phosphonate.

References Cited UNITED STATES PATENTS 2,900,408 8/1195-8 Blaser et a1. 260-946 XR CHARLES B. PARKER, Primary Examiner. A. H. SUTTO, Assistant Examiner. 

